Fuel cells are promising electrical power generation technologies, with key advantages including high efficiency and low pollution. Most potential near-term applications of fuel cells require the use of hydrocarbon fuels such as methane, for which a supply infrastructure is currently available. However, fuel cells typically operate only with hydrogen as the fuel. Thus, current demonstration power plants and planned fuel-cell electric vehicles must include a hydrocarbon fuel reformer to convert the hydrocarbon fuel to hydrogen. Fuel cells that could operate directly on hydrocarbon fuels would eliminate the need for a fuel reformer, providing considerable system and economic advantages and presumably improving the viability of the technology.
Prior art fuel cells utilizing hydrocarbon fuels directly have encountered significant problems. For example, direct-methanol polymer electrolyte fuel cells produce relatively low power densities and require prohibitively large Pt loading of the anodes. In addition, methanol can permeate the electrolyte. See, for instance, Ren, X., Wilson, M. S. and Gottesfeld, S. High performance direct methanol polymer electrolyte fuel cells. J. Electrochem. Soc., 143, L12-L14 (1996); and Wang, J., Wasmus. S. and Savinell, R. F. Evaluation of ethanol, 1-propanol, and 2-propanol in a direct oxidation polymer-electrolyte fuel cell a real-time mass spectrometry study. J. Electrochem. Soc., 142, 4218-4224 (1995). Furthermore, only alcohol fuels appear feasible with this approach.
Alternatively, prior art solid oxide fuel cells (SOFCs) can utilize hydrocarbons directly via internal or external reforming. In this approach, a hydrocarbon fuel (e.g., methane) is combined with H2O and/or CO2, which are typically obtained by recirculating the fuel cell exhaust, and introduced directly to the SOFC anode. Commonly used Ni-based anodes provide the catalyst for the endothermic reforming reactions,CH4+H2O=3H2+CO ΔH°298=206 kJ/mol CH4  (1)CH4+CO2=2H2+2CO ΔH°298=247 kJ/mol CH4  (2)However, maintaining appropriate gas composition and temperature gradients across a large area SOFC stack is challenging. See, Janssen, G. J. M., DeJong, J. P., and Huijsmans, J. P. P. Internal reforming in state-of-the-art SOFCs. 2nd European Solid Oxide Fuel Cell Forum, 163-172, Ed. by Thorstense, B. (Oslo/Norway, 1996); and Hendriksen, P, V., Model study of internal steam reforming in SOFC stacks. Proc. 5th Int. Symp. on Solid Oxide Fuel Cells, 1319-1325, Ed. by U. Stimming, S. C. Singhal, H. Tagawa, and W. Lehnert (Electrochem, Soc., Pennington, 1997).
For instance, if the reforming reactions are slow, then insufficient H2 is supplied to the SOFCs. On the other hand, fast reforming reactions cause cooling localized near the fuel inlet, leading to poor cell performance, and possible cell fracture. Thus, current SOFC stacks of the prior art do not take full advantage of internal reforming; rather, they employ a combination of ≈75% external and 25% internal reforming of hydrocarbon fuels. See, Ray, E. R. Westinghouse Tubular SOFC Technology, 1992 Fuel Cell Seminar, 415-418 (1992).
SOFCs can in principle operate directly by use of a hydrocarbon fuel. This approach would be desirable since it eliminates the problems with internal reforming mentioned above, and the theoretical maximum fuel efficiency is as good or better than that for reforming. However, prior art attempts with SOFCs operating at temperatures Tc=900-1000° C. with methane fuel have been less than satisfactory: either power densities were very low or carbon deposition was observed. See, Putna, E. S., Stubenrauch, J., Vohs, J. M. and Gorte, R. J. Ceria-based anodes for the direct oxidation of methane in solid oxide fuel calls, Langmuir 11, 4832-4837 (1995); and Aida, T., Abudala, A., Ihara, M., Komiyama, H. and Yamada, K. Direct oxidation of methane on anode of solid oxide fuel cell. Proc. 4th Int. Symp. on Solid Oxide Fuel Cells, 801-809, Ed. by Dokiya, M., Yamamoto, O., Tagawa, H. and Singhal, S. C, (Electrochem. Soc. Pennington, 1995).
Recently, SOFCs have been developed to produce high power densities with hydrogen at reduced temperatures, Tc=600-800° C. See, Huebner, W., Anderson, H. U., Reed, D. M., Sehlin, S. R. and Deng, X. Microstructure property relationships of NiZrO2 anodes. Proc. 4th Int. Symp. on Solid Oxide Fuel Cells, 696-705, Ed. by Dokiya, M., Yamamoto, O., Tagawa, H. and Singhal, S. C. (Electrochem. Soc. Pennington, 1995); daSouza, S., Visco, S J. and DeJonghe, L. C. Thin-film solid oxide fuel cell with high performance at low-temperature. Solid State Ionics 98, 57-61 (1997); Fung, K-Z., Chen, J., Tanner, C. and Virkar, A. V. Low temperature solid oxide fuel cells with dip-coated YSZ electrolytes. Proc. 4th Int. Symp. on Solid Oxide Fuel Cells, 1018-1027, Ed. by Dokiya, M., Yamamoto, O., Tagawa, H. and Singhal, S. C. (Electrochem. Soc. Pennington, 1995); Minh, N. Q. Development of thin-film solid oxide fuel cells for power generation applications. Proc. 4th Int. Symp. on Solid Oxide Fuel Cells, 138-145, Ed. by Dokiya, M., Yamamoto, O., Tagawa, H. and Singhal, S. C. (Electrochem. Soc. Pennington, 1995); Godickemeier, M., Sasaki, K. and Gauckler, L. J. Current-voltage characteristics of fuel cells with ceria-based electrolytes. Proc. 4th Int. Symp. on Solid Oxide Fuel Cells, 1072-1081, Ed. by Dokiya, M., Yamamoto, O., Tagawa, H. and Singhal, S. C. (Electrochem. Soc. Pennington, 1995); Tsai, T. and Barnett, S. A. Increased solid-oxide fuel cell power density using interfacial ceria layers. Solid State Ionics 98, 191-196 (1997); and Tsai, T., Perry, E. and Barnett, S. Low-temperature solid-oxide fuel cells utilizing thin bilayer electrolytes. J. Electrochem. Soc., 144, L130-L132 (1997). However, until recently, such systems were not considered or used for direct-hydrocarbon operation, because carbon deposition reaction rates decrease with decreasing temperature.
SOFCs and related stacking configurations have undergone considerable development over the past decade. Tubular-cell-based technologies appear to be a promising approach for SOFC stacking. Tubular stacks avoid sealing and manifolding problems inherent to planar stacks, but take a large volume for a given cell active area and can show significant ohmic losses related to current transport around the tube circumference through the (La,Sr)MnO3 (LSM) cathode. Another problem is the relatively poor mechanical toughness of LSM.[N. M. Sammes, R. Ratnaraj, and C. E. Hatchwell, Proceedings of the 4th International Symposium on Solid Oxide Fuel Cells, Ed. By Dokiya, O. Yamamota, H. Tagawa, and S. C. Singhal (Electrochemical Society, Pennington, 1995) p. 952. B. Krogh, M. Brustad, M. Dahle, J. L. Eilertsen, and R. Odegard, Proceedings of the 5th International Symposium on Solid Oxide Fuel Cells, Ed. By U. Stimming, S. C. Singhal, H. Tagawa, and W. Lehnert (Electrochemical Society, Pennington, 1997) p. 1234.] This is typical of SOFC ceramic materials, which are optimized for electrical properties rather than mechanical toughness.
Alternatively, planar stacks can provide higher power-to-volume ratios than tubular stacks, but are not as mechanically robust as tubes and require excellent seals. Another problem with many planar stack designs is that they require pressure contacts between separate SOFC and interconnect plates. This places stringent requirements on the flatness of large-area ceramic plates, making manufacturing difficult and expensive. Furthermore, there are often relatively high resistances associated with these contacts, which deleteriously affect stack performance. It is clear that a choice between tubular and planar stacks involves trade-offs. Even so, the disadvantages associated with each respective approach present obstacles for effective use of SOFCs and suggest a new direction is needed to better utilize and benefit from this technology.